Apparatus and method for depositing a coating on a substrate at atmospheric pressure

ABSTRACT

An apparatus for depositing a coating on a substrate at atmospheric pressure comprises (a) a plasma torch comprising a microwave source coupled to an antenna disposed within a chamber having an open end, the chamber comprising a gas inlet for flow of a gas over the antenna to generate a plasma jet; (b) a substrate positioned outside the open end of the chamber a predetermined distance away from a tip of the antenna; and (c) a target material to be coated on the substrate disposed at the tip of the antenna.

RELATED APPLICATION

The present patent document is a division of U.S. patent applicationSer. No. 14/657,327, filed Mar. 13, 2015, which claims the benefit ofpriority under 35 U.S.C. § 119(e) to U.S. Provisional Patent ApplicationNo. 61/953,072, filed on Mar. 14, 2014, both of which are herebyincorporated by reference in their entirety.

TECHNICAL FIELD

The present disclosure is related generally to vapor deposition and moreparticularly to forming coatings at atmospheric pressure.

BACKGROUND

Low-pressure plasmas (LPPs) have been widely investigated and have founda number of applications in semiconductor manufacturing and processing.A relatively large and uniform plasma has to be sustained and confinedin a vacuum system in order to achieve a uniform processing rate acrossthe whole chamber. The benefit of LPP is that it requires a lowbreakdown voltage to ignite and has a relatively high electrontemperature and low neutral temperature. However, a vacuum system isrequired to generate a plasma in a low pressure environment. Vacuumsystems, including the chamber, pumps and other related componentsinside the chamber, can be expensive and difficult to adapt to changesin application requirements. Semiconductor processes, such as plasmaetching and plasma deposition, can also create contamination in thevacuum chamber that may require constant cleaning, repair andmaintenance.

Evaporation has also been widely used to make coatings on materials. Atypical evaporator uses a small electron beam to heat the surface of thematerial which is to be used as the coating until it evaporates. Simplyheating a crucible is another way of raising the temperature high enoughsuch that sufficient material enters the vapor phase. These techniquesalso require a vacuum system since the electron beam, and moreimportantly the evaporated vapor, would otherwise have so manycollisions in the background gas that they could not reach theirintended targets.

Atmospheric pressure plasmas can be categorized into several types,according to the configuration. First is the corona discharge, which isusually ignited by applying a DC voltage (˜10 kV) between a pointelectrode and a plane electrode. The distance is at the scale of severalmm, and the current is usually kept low (<300 μA) to prevent arcing. Thesecond is the dielectric barrier discharge (DBD), which is usuallygenerated between two metal electrodes, where one or both are coatedwith a dielectric layer and may have a spacing of several millimeters.Generation of DBDs in general requires a 10 to 20 kV DC voltage, and theplasma can be spread relatively evenly in a large area. Finally, thereis the atmospheric pressure plasma jet (APPJ). It may include twoconcentric electrodes, where the inner one may be applied with a 13.56MHz RF power or a 2.45 GHz microwave power. Gases with adjustable ratesare introduced between the two electrodes during the discharge. Theignition condition for an APPJ can be easily achieved, and the dischargeof an APPJ may be homogenous, volumetric and low in gas temperature.However, sustaining a gas discharge at atmospheric pressure may be moredifficult than in a vacuum chamber, since time constants forinstabilities decrease with increasing pressure. A simple approach togenerate large-volume atmospheric-pressure plasmas may be to create alarge electric field around the cathode boundary region to supplysufficient production of electrons, which may depend on the specificstructure of the electrodes and type of feed gas.

A comparison of the breakdown voltage and electron density of differentatmospheric-pressure plasmas and low-pressure plasmas are listed inTable 1. It can be seen that APPJs have similar breakdown voltage to thelow pressure discharges, which can be one to three orders of magnitudelower than the other atmospheric-pressure discharges. At the same time,the electron densities of APPJs are also in the same range oflow-pressure discharges, but lower than the rest of atmospheric pressuredischarges.

TABLE 1 Breakdown voltage and electron density of plasma discharges.Electron density Plasma Source Breakdown voltage (kV) (cm⁻³) Lowpressure discharge 0.2-0.8  10⁸-10¹³ Arc 10-50 10¹⁶-10¹⁹ Corona 10-50 10⁹-10¹³ DBD  5-25 10¹²-10¹⁵ APPJ 0.05-0.2  10¹¹-10¹²

BRIEF SUMMARY

An apparatus for depositing a coating on a substrate at atmosphericpressure comprises (a) a plasma torch comprising a microwave sourcecoupled to an antenna disposed within a chamber having an open end, thechamber comprising a gas inlet for flow of a gas over the antenna togenerate a plasma jet; (b) a substrate positioned outside the open endof the chamber a predetermined distance away from a tip of the antenna;and (c) a target material to be coated on the substrate disposed at thetip of the antenna.

A method of depositing a coating on a substrate at atmospheric pressurecomprises immersing a target material within a microwave plasma jet atatmospheric pressure; removing atoms from the target material, the atomsbeing transported from the target material to a substrate by themicrowave plasma jet; and forming a coating on the substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1E show schematics of various embodiments of an atmosphericpressure plasma torch (APPT) powered by a microwave generator forevaporative coating at atmospheric pressure (ECAP).

FIG. 2 shows a more detailed schematic of the plasma torch shown in FIG.1A, where the dimensions are shown in inches.

FIG. 3 shows a more detailed schematic of the antenna shown in FIG. 1A,wherein the dimensions are shown in inches.

FIG. 4 shows a transmission electron microscope (TEM) image of anexemplary alumina coating formed by ECAP using a plasma torch operatingat 800 W of power. A mix of amorphous and crystalline structure may beobserved in the image.

FIG. 5A shows a COMSOL simulation image for the gas flow profile insidean exemplary atmospheric pressure plasma jet.

FIG. 5B shows gas flow velocity at the antenna tip according to theCOMSOL simulations, where mass flow velocity is plotted as a function ofinput mass flow.

FIG. 6 shows predicted temperature at the substrate center and maximumplasma temperature according to the COMSOL simulations.

DETAILED DESCRIPTION

For the first time, thin films having a controlled microstructure havebeen created by a microwave-powered plasma jet under atmosphericpressure conditions. The basic principle behind this technique, whichmay be referred to as evaporative coating at atmospheric pressure(ECAP), is to use heat from a plasma to melt and evaporate a targetcomprising a source material (e.g., metal) at the tip of an antennawhere the plasma is generated at atmospheric pressure. Vaporized atomsare carried by a gas flow (e.g., He and N₂ or Ar) in the plasma towardsa substrate surface, where they deposit and adhere atom-by-atom orcluster-by-cluster. If the deposited atoms or clusters (e.g.,nanocrystals) comprise a reactive material such as a metal, the atoms orclusters may be oxidized by atmospheric oxygen to form metal oxidecoatings, or by other gases to create other compounds (e.g., by nitrogento make metal nitrides).

Among the benefits of this technology are that the phase and morphologyof the deposited material may be modified by changing the plasmaconditions. Also, since the process takes place at atmospheric pressure,no expensive vacuum chamber or vacuum equipment is needed, and highdeposition rates can be achieved. Additionally, the process can be usedfor deposition on non-planar surfaces by moving the substrate withrespect to the plasma torch, or by moving the torch at the end of a5-axis robot to coat a complicated shape in the field.

As shown in FIGS. 1A-1E, an apparatus for depositing a coating on asubstrate at atmospheric pressure includes: a plasma torch 100comprising a microwave source 105 coupled to an antenna 120 disposedwithin a chamber 125 having an open end 125 a, where the chamber 125comprises a gas inlet 140 for flow of a gas over the antenna 120 togenerate a plasma jet. A substrate 150 is positioned outside the openend 125 a of the chamber 125 a predetermined distance away from a tip ofthe antenna 120, and a target material 145 to be coated on the substrate150 is disposed at the tip of the antenna 120.

Referring to FIG. 1A, the plasma torch 100 is powered by a microwavesource 105, such as a 2.45 GHz microwave generator available from CoberElectronics, Inc. (Model S64). Microwaves are generated by a magnetronsupplied with a 12 kW power input and having an output that varies fromapproximately 0.5 to 6 kW into a matched load with continuouslyadjustable power. A waveguide 110 such as the WR 284 waveguide cavity isused to transmit microwave power from the magnetron 105 to theatmospheric torch 100. A coaxial adapter 115 is used to couple themicrowave from the waveguide 110 into the antenna 120 of the plasmatorch 100.

The plasma torch 100 may have a coaxial cylinder design with adecreasing diameter near the top of the torch, as can be seen in FIG.1A. The chamber or resonator body 125 may be made from copper, and theantenna 120 may be fabricated from tungsten and connected to the coaxialadapter 115 by, for example, a receptacle jack made by Huber & SuhnerGroup, USA and a 7/16 DIN adapter by RF Parts Company, USA. A gas may befed into the APPT 100 from a gas inlet 140 near the bottom of theresonator body 125, which may be grounded. A Teflon pad 135 may beplaced at the base of the wall of the outermost cylinder wall in orderto prevent arcing between the antenna 120 and the copper chamber 125. Amore detailed schematic of one embodiment of the plasma torch 100 ofFIG. 1A is shown in FIG. 2, with dimensions shown in inches.

The antenna 120 may have a neck or taper 120 a near the top to reduceheat loss to the base of the antenna 120. The antenna 120 may be ¼ inchin diameter and 6¼ inches in length, or, more generally, from about 1/64inch (0.4 mm) to about 2 inches (50.8 mm) in diameter and may have alength that depends on the height of the chamber, which may range fromabout 2.5 inches (63.5 mm) to about 25 inches (635 mm). A targetmaterial 145 may be positioned at the tip of the antenna 120. The torch100 may include a quartz discharge tube 130 surrounding the antenna 120and defining a pathway for gas flow over the antenna 120. In oneexample, the quartz discharge tube may have an outer diameter of 16.2 mmand an inner diameter of 13 mm (Technical Glass Products, Inc., USA).The quartz discharge tube 130 may be fixed within the torch 100 by twoTeflon rings disposed between the discharge tube 130 and the coppercylinders 125. A substrate 150 that may be in a substrate holder 155 isplaced a short distance away from the torch 100 for deposition of thecoating. For example, the substrate 150 is typically spaced apart fromthe tip of the antenna and/or the target material by about 1/32 inch(0.8 mm) to about 2 inches (50.8 mm).

The microwave waveguide 110 may include five primary sections: (1) analuminum 90° E-bend or H-bend, depending on the experimentalrequirements, to change the direction of the microwave propagation fromvertical to parallel; (2) a two-port circulator with an embedded waterload to ensure that the reflected microwave is absorbed in the waterload instead of traveling back to the magnetron; (3) a dual directionalcoupler 110 a, which may have a 60 dB power attenuation at both portsfor detecting forward and reflected microwave power respectively; (4) a3-stub or 4-stub tuning system 110 b, which can continuously adjust thereflected microwave power by inserting or extracting one or more tuningstubs in order to change the impedance matching and keep the reflectedmicrowave power to less than 5% of the output power; and (5) a coaxialadapter 115 (e.g., a WR 284 to 7/16 coaxial adapter), which couples themicrowave from the waveguide cavity into the antenna of the plasmatorch. The aluminum E-bend, H-bend, two-port circulator, dualdirectional coupler, 4-stub tuning system may be obtained fromCoberMuegge LLC, USA, while the 3-stub tuning system and the WR284 to7/16 adapter used in the exemplary apparatus were custom made at theUniversity of Illinois at Urbana-Champaign.

Several alternative embodiments of the atmospheric pressure plasma torch(APPT) are shown in FIGS. 1B-1E. During the ECAP process, a gas shieldor curtain may be formed to help prevent oxidation of the evaporatedmaterial as it travels to the substrate. To generate the gas shieldduring operation of the plasma torch 100, a cylindrical nozzle 165 maybe positioned radially outside the quartz tube 130 to direct anonreactive gas into a region surrounding the plasma 160, as shown inFIG. 1B. The nozzle 165 includes a gas inlet 170 a and an annular outlet170 b to direct exiting gas to the substrate 150. The nozzle 165 mayhave a length selected to position the outlet 170 b of the nozzle 165 atthe desired distance from the substrate 150.

FIG. 1C shows an embodiment of the APPT in which an arc source is addedto the apparatus to provide additional heating of the target materialand decouple the temperature needed for evaporation of the target fromthe temperature of the plasma. The plasma torch 100 includes a first arcpower input 175 for an external electrode 170 and a second arc powerinput 185 for an internal electrode 180 separated from the externalelectrode 170 by a ceramic tube 190. A ceramic disk 195 electricallyisolates the internal electrode 180 from the first arc power input 175.The other components of the apparatus 100 are as described above. Inuse, an arc discharge may be generated between the internal and externalelectrodes 170,180 prior to igniting the plasma. For example, a voltageof from about 10 V to 60 V and a current of 5 A to 250 A may be used topower the arc source. The external electrode 170 is in electricalcontact with the antenna 120 and thus also functions as the antenna 120,the antenna having the tip at which the target material is disposed.

FIG. 1D shows an embodiment of the APPT that combines the plasma torch100 with a nozzle 165 for generating the gas shield and an arc sourceincluding internal and external electrodes 170,180 and respective powerinputs 175,185, as shown. FIG. 1E shows an embodiment of the APPT thatincludes a continuous feed of the target material 145 a through a hollowcore of the antenna 120. In this embodiment, the target material 145 amay take the form of a wire, powders, a series of pellets, or a melt.The continuous feed of the target material 145 a may be incorporatedinto any of the embodiments of the APPT described above.

The APPT described herein can generate an atmospheric pressure plasmahaving a plasma gas temperature ranging from room temperature to amaximum of about 3000° C., depending on the applied power, gas flow rateand the type of processing gases introduced. Using helium, the plasmatypically can self-ignite to generate an atmospheric pressure plasmawith a gas flow of between 10-30 liters per minute (LPM). If desired, anigniter can be placed on the tip of the antenna to facilitate plasmaignition. The igniter may comprise a sharp metal wire (usually tungstenor copper) with a ceramic insulator break. A plasma based on argon,nitrogen or air may be obtained by first igniting a helium plasma, thenmixing one or more of the desired gases into the helium gas flow, andthen slowly turning off the flow of helium gas. The ECAP process maytake place for a time duration of between about 1 minute and tens ofhours.

Each of the processing gases (e.g., helium, argon, nitrogen, oxygen,hydrogen, etc.) may be controlled using a flow meter, such as aRMA-Master flow meter made by Dwyze Instruments, Inc., USA. The flowmeters can be individually controlled in order to produce different gasmixtures to generate different types of plasma. In the examplesdescribed here, helium and nitrogen are used primarily to create theplasma profile and gas temperature employed for the evaporation anddeposition process. However, any inert gas (e.g., He, Ar, Ne, etc.) maybe suitable if it is desired to produce a coating having substantiallythe same composition as the target material. It is also contemplatedthat a reactive gas may be used to generate the plasma jet (eitherinstead of or in addition to the inert gas) in order to form an oxide ornitride coating, for example, from the target material.

Typically, a target material having a boiling (evaporation) point at orbelow the temperature achieved by the plasma is employed. The targetmaterial may comprise a metal such as: Al, Au, Sn, Ag, Fe, Ti, and/orothers that have a melting point below tungsten. In the examplesdescribed here, a 99.99%+ pure aluminum target obtained from Kurt J.Lesker Co. is used. It is thus preferred that the target material has apurity of at least about 99.9%, at least about 99.99%, or at least about99.999%. The target may take the form of a monolithic solid body ofmaterial, or it may comprise pellets or particles of the material. Forexample, the target may take the form of cylindrical aluminum pellets of⅛ inch (3.2 mm) in diameter and ⅛ inch (3.2 mm) in height. Aluminumpellets having a high purity are preferred, since the deposition rate ofaluminum oxide decreases as the impurity level of the target increases.In tests of 1000 series aluminum alloy (99% pure aluminum) pellets, thedeposition rates were close to negligible.

An exemplary antenna 120 for the APPT is shown in greater detail in FIG.3. In this example, the antenna is fabricated from 99.95% pure tungstenwith a diameter of ¼ inch (6.4 mm), and about 6.5 inches (165 mm) totalin length. The antenna may include a cup or recess 120 a at one end tosupport the target material. Referring to FIG. 3, the cup 120 a in theexemplary antenna 120 shown in the figure is about 0.08 inch (2.0 mm) indepth and 0.2 inch (5.1 mm) in diameter. The diameter of the cup 120 ais made slightly larger than the size of the target material toaccommodate molten material during and after the evaporation and coatingprocess, so that overflows at the antenna tip may be avoided. Theantenna 120 may also include a bottleneck 120 b to reduce the thermalconductivity and thus heat loss from the tip, where the plasma isgenerated, to the base of the antenna 120. In the exemplary antenna 120of FIG. 3, the bottleneck 120 b is constructed about ⅛ inch (3.2 mm)below the tip of the tungsten antenna 120, where the diameter of theantenna 120 is reduced from about ¼ inch (6.4 mm) to about 0.1 inch (2.5mm) over a length of about 0.1 inch (2.5 mm).

According to Fourier's law: dQ/dt=−UAΔT, where dQ/dt is the amount ofheat transferred per unit time in W, U is the conductance in W/m²K, A isthe cross-sectional area in square meters and ΔT is the temperaturedifference between the two ends in Kelvin. By reducing the diameter ofthe antenna from 0.25 inch (6.4 mm) to 0.1 inch (2.5 mm) at the neck,the heat lost through the antenna is reduced by about 84%(1−(0.1/0.25)²). This design can effectively increase the targettemperature with the same input power, or achieve the same targettemperature with a lower input power, thereby increasing processefficiencies and reducing microwave leakage. An insulating material suchas zirconium oxide may also be placed in between the target and theantenna to further insulate the target and reduce heat lost to theantenna.

Advantageously, the substrate 150 used for deposition of the coating cansustain high gas temperatures and remain chemically inert. For example,the substrate may comprise a metal or alloy, such as 304 stainlesssteel. The substrate may be machined to the desired size and mountedonto a substrate support or mount. It is also contemplated that lowertemperature materials may be employed for the substrate, such aspolymers or paper. In examples carried out here, the substrate is chosento be about 1 inch (25.4 mm) in diameter to provide a large surface areafor coating yet easily fit into various stage holders for thin-filmcharacterization, such as scanning electron microscopy (SEM), x-raydiffraction (XRD), and x-ray photoelectron spectroscopy (XPS). However,the substrate may have any desired size ranging from about 10 mm indiameter to many meters, if the substrate is continuously moving withrespect to the torch.

Aluminum targets have been evaporated using microwave atmosphericpressure plasma jet in ECAP experiments. It has been demonstrated thataluminum oxide can be successfully coated onto 304 stainless steelsubstrates using a helium and nitrogen gas mix and an atmosphericpressure microwave plasma. Preferably, a high purity aluminum target isemployed to produce the desired aluminum oxide coating at a satisfactoryrate. The film morphology is found to be porous under low powerdeposition but denser under higher power deposition conditions. δ phaseand β phase alumina are found in a coating prepared at 800 W sample andβ phase and α phase alumina are found in a coating prepared at 1500 W.The phase of the deposited alumina film is determined to vary accordingto changes in input microwave power, and more than one phase of aluminamay be simultaneously formed in the alumina film, in the form ofnanocrystals that may be identified using transmission electronmicroscopy (TEM), as shown for example in FIG. 4.

The plasma formed in ECAP is highly collisional and away fromequilibrium. Also, the electron-neutral collision frequency is muchgreater than the plasma frequency at atmospheric pressure. Therefore,traditional characterization methods such as Langmuir probe diagnosticsmay not work for measuring electron temperature, electron density, orparticle distribution of the plasma. Thus, to better understand theplasma and gas condition in the APPJ during operation, COMSOL finiteelement analysis simulation software is used to simulate the plasma gastemperature and the gas flow in the plasma region and inside themicrowave torch during operation. The Reynolds number is calculated tobe around 3000 and the flow inside the APPJ is found to be in turbulentregime. The standard turbulent flow kappa epsilon model is used to modelthis turbulent flow inside the APPJ, and the flow profile is found topeak around the antenna tip. FIG. 5A shows a COMSOL simulation image forthe gas flow profile inside an exemplary atmospheric pressure plasmajet. The highest rate of flow (about 0.9 m/s) is located at the areaoutside the tip of the antenna. Mass flow velocity is plotted as afunction of input mass flow in FIG. 5B. By coupling the turbulent flowmodel and the RF microwave heating model, the dielectric heating insidethe APPJ and thus the temperature profile may be simulated. Referring toFIG. 6, the temperature profile is found to be close to the boilingpoint of alumina at the target surface and below melting point of the304 stainless steel at the substrate surface. The temperature profilealso correctly predicts the different phases obtained for samplesprepared with different input microwave power.

Although the present invention has been described in considerable detailwith reference to certain embodiments thereof, other embodiments arepossible without departing from the present invention. The spirit andscope of the appended claims should not be limited, therefore, to thedescription of the preferred embodiments contained herein. Allembodiments that come within the meaning of the claims, either literallyor by equivalence, are intended to be embraced therein.

Furthermore, the advantages described above are not necessarily the onlyadvantages of the invention, and it is not necessarily expected that allof the described advantages will be achieved with every embodiment ofthe invention.

The invention claimed is:
 1. An apparatus for depositing a coating on asubstrate at atmospheric pressure, the apparatus comprising: a plasmatorch comprising: a microwave source coupled to an antenna disposedwithin a chamber, the antenna being a linear antenna, the chamber havingan open end and comprising a gas inlet for flow of a gas over theantenna to generate a plasma jet; and an arc source comprising aninternal electrode separated from an external electrode, the externalelectrode being in electrical contact with a first arc power input, andthe internal electrode being in electrical contact with a second arcpower input, the internal and external electrodes being tubular andextending linearly; the external electrode being in electrical contactwith the antenna, and also functioning as the antenna, the antennahaving a tip; a substrate positioned outside the open end of thechamber, and disposed a predetermined distance away from the tip of theantenna; and a target material, that is different from the gas, to becoated on the substrate disposed at the tip of the antenna.
 2. Theapparatus of claim 1, further comprising a discharge tube surroundingthe antenna and defining a pathway for gas flow over the antenna.
 3. Theapparatus of claim 2, further comprising a cylindrical nozzle disposedradially outside the discharge tube to direct a flow of nonreactive gasinto a region surrounding the plasma jet.
 4. The apparatus of claim 1,wherein the antenna comprises a hollow core, and wherein the targetmaterial comprises a continuous feed to the tip of the antenna throughthe hollow core.
 5. The apparatus of claim 1, wherein the predetermineddistance between the substrate and the tip of the antenna is from about0.8 mm to about 51 mm.
 6. The apparatus of claim 1, wherein the chamberis grounded.
 7. The apparatus of claim 1, wherein the target materialincludes one or more elements selected from the group consisting of: Al,Au, Sn, Ag, Ti, Fe, and Cr.
 8. An apparatus for depositing a coating ona substrate at atmospheric pressure, the apparatus comprising: a plasmatorch comprising: a microwave source coupled to an antenna disposedwithin a chamber, the antenna being a linear antenna, the chamber havingan open end and comprising a gas inlet for flow of a gas over theantenna to generate a plasma jet, and the antenna comprising a hollowcore; an arc source comprising an internal electrode separated from anexternal electrode, the external electrode being in electrical contactwith a first arc power input, and the internal electrode being inelectrical contact with a second arc power input, the internal andexternal electrodes being tubular and extending linearly; the externalelectrode being in electrical contact with the antenna, and alsofunctioning as the antenna, the antenna having a tip; a substratepositioned outside the open end of the chamber, and disposed apredetermined distance away from the tip of the antenna; and a targetmaterial that is different from the gas, to be coated on the substratedisposed at the tip of the antenna, the target material comprising acontinuous feed to the tip of the antenna through the hollow core. 9.The apparatus of claim 8, further comprising a discharge tubesurrounding the antenna and defining a pathway for gas flow over theantenna.
 10. The apparatus of claim 9, further comprising a cylindricalnozzle disposed radially outside the discharge tube to direct a flow ofnonreactive gas into a region surrounding the plasma jet.
 11. Theapparatus of claim 8, wherein the chamber is grounded.
 12. The apparatusof claim 8, wherein the target material includes one or more elementsselected from the group consisting of: Al, Au, Sn, Ag, Ti, Fe, and Cr.